TWI740122B - Surface treatment method of wafer and composition used in the method - Google Patents
Surface treatment method of wafer and composition used in the method Download PDFInfo
- Publication number
- TWI740122B TWI740122B TW108111659A TW108111659A TWI740122B TW I740122 B TWI740122 B TW I740122B TW 108111659 A TW108111659 A TW 108111659A TW 108111659 A TW108111659 A TW 108111659A TW I740122 B TWI740122 B TW I740122B
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- Taiwan
- Prior art keywords
- composition
- wafer
- water
- protective film
- group
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 194
- 238000000034 method Methods 0.000 title claims abstract description 73
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- 230000001681 protective effect Effects 0.000 claims abstract description 87
- 238000004140 cleaning Methods 0.000 claims abstract description 68
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
- B08B7/0014—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by incorporation in a layer which is removed with the contaminants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
本發明係提供一種蒸氣處理用之新穎組合物、及使用該新穎組合物之蒸氣的具有Si元素之晶圓之表面處理方法，該新穎組合物係撥水性保護膜形成成分之種類更少者，其可發揮與利用先前之(撥水性保護膜形成成分之種類較多之)組合物之蒸氣進行具有Si元素之晶圓表面之處理之情形同等之撥水性賦予效果，化學穩定性優異。本發明之晶圓之表面處理方法之特徵在於：其係於表面具有凹凸圖案，且至少於該凹部具有Si元素之晶圓之洗淨中，於上述凹凸圖案之至少凹部保持有液體之狀態下，將含有撥水性保護膜形成成分與溶劑之組合物之蒸氣供給至上述凹凸圖案表面，使上述蒸氣之狀態變為液體狀態，將保持於上述凹部之液體置換為該組合物之液體，從而至少於上述凹部表面形成撥水性保護膜之方法；且上述撥水性保護膜形成成分僅為下述通式[1]所表示之化合物，上述溶劑至少含有非環狀碳酸酯，溶劑總量中之上述非環狀碳酸酯之量為50～100質量%。 [化5] R1 x (CH3 )3-x SiN(R2 )2 [1] [式[1]中，R1 分別獨立為選自H基、碳數為1～10之烴基、及氫原子之一部分或全部被氟原子取代之碳數為1～10之烴基之基；x為1～3之整數。R2 分別相互獨立為選自氫原子之一部分或全部可被氟原子取代之甲基、乙基、乙醯基之基]。The present invention provides a novel composition for steam treatment and a method for surface treatment of a wafer with Si element using the steam of the novel composition. The novel composition is a water-repellent protective film forming component having fewer types It can exert the same effect of imparting water repellency as in the case of treating the surface of a wafer with Si element using the vapor of the previous composition (there are many types of water repellent protective film forming components), and has excellent chemical stability. The surface treatment method of the wafer of the present invention is characterized in that it has a concave-convex pattern on the surface, and at least in the cleaning of a wafer with Si element in the concave portion, in a state in which at least the concave portion of the concave-convex pattern is kept in a liquid state , The vapor of the composition containing the water-repellent protective film forming component and the solvent is supplied to the surface of the concave-convex pattern, the state of the vapor is changed to a liquid state, and the liquid held in the concave portion is replaced with the liquid of the composition, thereby at least A method for forming a water-repellent protective film on the surface of the concave portion; and the water-repellent protective film forming component is only a compound represented by the following general formula [1], the solvent contains at least acyclic carbonate, and the total amount of the solvent The amount of acyclic carbonate is 50-100% by mass. [Chemical 5] R 1 x (CH 3 ) 3-x SiN(R 2 ) 2 [1] [In formula [1], R 1 is each independently selected from H group, hydrocarbon group having 1 to 10 carbon atoms, and A hydrocarbon group with 1-10 carbon atoms in which part or all of the hydrogen atoms are replaced by fluorine atoms; x is an integer of 1-3. R 2 are each independently a group selected from a methyl group, an ethyl group, and an acetyl group in which part or all of the hydrogen atoms can be substituted by fluorine atoms].
Description
本發明係關於一種於具有Si元素之晶圓之洗淨中，將特定之組合物之蒸氣使用於撥水性保護膜之形成中的晶圓之表面處理方法及該組合物。The present invention relates to a method for surface treatment of wafers in the process of washing wafers with Si elements, using vapor of a specific composition in the formation of a water-repellent protective film, and the composition.
於網路或數位家電用之半導體元件中，要求進一步之高性能、高功能化、或低耗電化。因此，正在進行電路圖案之微細化，伴隨著微細化之進行，電路圖案之圖案崩塌成為問題。於半導體元件製造中，多使用以去除微粒或金屬雜質為目的之洗淨步驟，其結果洗淨步驟占到半導體製程全體之3～4成之多。於該洗淨步驟中，若伴隨著半導體元件之微細化的圖案之縱橫比變高，則於洗淨或沖洗後，當氣液界面通過圖案時圖案發生崩塌之現象即為圖案崩塌。為了防止圖案崩塌之發生而不得不變更圖案之設計，且隨之會造成生產時之良率降低等，因此期待防止洗淨步驟中之圖案崩塌之方法。In semiconductor devices used in Internet or digital home appliances, further high performance, high functionality, or low power consumption are required. Therefore, the miniaturization of circuit patterns is progressing, and along with the progress of miniaturization, pattern collapse of the circuit patterns becomes a problem. In the manufacture of semiconductor devices, cleaning steps for the purpose of removing particles or metal impurities are often used. As a result, the cleaning steps account for 30 to 40% of the total semiconductor manufacturing process. In this cleaning step, if the aspect ratio of the pattern accompanying the miniaturization of the semiconductor device becomes higher, the phenomenon that the pattern collapses when the gas-liquid interface passes through the pattern after cleaning or washing is the pattern collapse. In order to prevent the occurrence of pattern collapse, the design of the pattern has to be changed, and consequently, the yield rate during production will decrease. Therefore, a method of preventing the pattern collapse in the cleaning step is expected.
作為防止圖案崩塌之方法，已知有於圖案表面形成撥水性保護膜之方法較有效。該撥水化需要於未使圖案表面乾燥之情況下進行，因此向保持有洗淨液等狀態之圖案表面供給可使該圖案表面撥水化之撥水性保護膜形成用藥液，自洗淨液等置換為上述藥液，藉此形成撥水性保護膜。As a method of preventing the pattern from collapsing, it is known that a method of forming a water-repellent protective film on the surface of the pattern is effective. The water repellency needs to be carried out without drying the pattern surface, so a water-repellent protective film forming chemical, self-cleaning liquid, which can make the pattern surface water repellent, is supplied to the pattern surface that is kept in a state of washing liquid, etc. Replace it with the above-mentioned chemical solution, thereby forming a water-repellent protective film.
於專利文獻1中揭示有一種藥液、及使用其之晶圓之處理方法，該藥液之特徵在於：其係用以於表面具有微細之凹凸圖案之矽晶圓之洗淨時，於該凹凸圖案表面形成撥水性保護膜之藥液；且上述藥液係當將OH基導入至凹凸圖案表面後，以蒸氣之形式供給至凹凸圖案表面者；其含有93.5～97.499質量%之選自由氫氟醚、氫氯氟烴所組成之群的至少1種以上含氟溶劑，2～5質量%之丙二醇單甲醚乙酸酯，0.5～5質量%之選自由六甲基二矽氮烷、四甲基二矽氮烷所組成之群之至少1種以上矽氮烷化合物，及0.001～0.25質量%之選自由三氟乙酸、三氟乙酸酐、三甲矽烷基三氟乙酸酯所組成之群之至少1種以上酸。
於專利文獻2中揭示有藉由含有各種矽烷化劑(三烷基矽烷基胺)與以碳酸酯類為主之溶劑的表面處理劑，對Si、SiO2
、SiN等各種狀態之基板表面有效地進行疏水化；且列舉有噴霧塗佈、旋轉塗佈、或浸漬作為於基板上塗佈表面處理劑之方法；且揭示有一種藉由浸漬而於基板上塗佈表面處理劑之實施例。
於專利文獻3中揭示有一種藉由加熱使碳酸二烷基酯、碳酸二芳基酯等非環狀碳酸酯、三級胺、與水反應而生成四級銨鹽之方法。
於非專利文獻1中報告有若於鹼性觸媒之存在下，使環狀碳酸酯與具有活性氫之有機化合物反應，則生成聚合物之現象。
先前技術文獻
專利文獻In
專利文獻1：日本專利第5648053號公報 專利文獻2：日本專利特開2013-168583號公報 專利文獻3：日本專利特開昭63-132862號公報 非專利文獻Patent Document 1: Japanese Patent No. 5648053 Patent Document 2: Japanese Patent Laid-Open No. 2013-168583 Patent Document 3: Japanese Patent Laid-Open No. 63-132862 Non-patent literature
非專利文獻1：Industrial & Engineering Chemistry Research(美利堅合眾國)，American Chemical Society，2003年，第42卷，第4號，p.663-674Non-Patent Document 1: Industrial & Engineering Chemistry Research (United States of America), American Chemical Society, 2003, Vol. 42, No. 4, p. 663-674
[發明所欲解決之問題][The problem to be solved by the invention]
專利文獻1中所記載之晶圓之處理方法係藉由蒸氣處理一次性地實施複數片之晶圓之表面處理，對於半導體晶圓之洗淨製程之效率化而言有效之方法。The wafer processing method described in
但是，本發明人等進行了研究，結果明確了以蒸氣之形式導入之藥液之組成、與作用於基板之組成未必相同。即，當於基板上狀態變為液體狀態時，狀態變化後之組成根據混合物之氣液平衡而定，因此雖然蒸氣壓較低之成分相對地高濃度化而使狀態變為液體狀態，但另一方面，氣相側變為富有低蒸氣壓成分之組成。因此，於處理裝置內，存在所導入之藥液蒸氣隨著於基板附近流通而造成組成發生變化之傾向。However, the inventors of the present invention conducted research, and as a result, it was found that the composition of the chemical liquid introduced in the form of vapor is not necessarily the same as the composition acting on the substrate. That is, when the state on the substrate becomes a liquid state, the composition after the state change is determined by the gas-liquid balance of the mixture. Therefore, although the component with a lower vapor pressure is relatively high in concentration, the state becomes a liquid state. On the one hand, the gas phase side becomes a composition rich in low vapor pressure components. Therefore, in the processing device, the introduced chemical liquid vapor tends to change its composition as it circulates near the substrate.
於專利文獻1所記載之處理方法中使用的藥液藉由如下方式而解決問題：作為除溶劑以外之「形成撥水性保護膜的必須成分(以後，有時記載為「撥水性保護膜形成成分」)」，使用將與凹凸圖案表面之OH基反應而形成撥水性保護膜之「矽氮烷化合物」、與促進該反應之「酸」之至少2種成分設為特定組成比的組合物。但是，如上所述地存在處理裝置內實際起作用之組成(尤其是「矽氮烷化合物」與「酸」之含量)隨著上述之流通而變化之虞，其結果存在對晶圓表面賦予撥水性之效果產生不均之虞。The chemical solution used in the treatment method described in
就降低如上所述地實際作用於晶圓表面之組成(於晶圓表面成為液體狀態之藥液組成)之不均之觀點而言，關於以蒸氣之形式導入之藥液之組成，較理想為撥水性保護膜形成成分之種類較少之組合物，尤其較理想為使用即便是無觸媒(反應促進成分)之體系亦發揮與專利文獻1所記載之藥液同等之撥水性賦予效果的撥水化劑。又，就維持表面處理氣氛或作為表面處理對象之晶圓之清潔性之觀點而言，期待該藥液化學穩定性優異。From the viewpoint of reducing the unevenness of the composition actually acting on the wafer surface as described above (the composition of the chemical liquid that becomes a liquid on the wafer surface), the composition of the chemical liquid introduced in the form of vapor is preferably Water-repellent protective film-forming components have fewer types of compositions, and it is particularly desirable to use a water-repellent imparting effect equivalent to that of the drug solution described in
因此，本發明之課題在於提供解決上述問題之組合物、及提供於具有Si元素之晶圓之洗淨中將該組合物之蒸氣使用於撥水性保護膜之形成中的晶圓之表面處理方法。 [解決問題之技術手段]Therefore, the subject of the present invention is to provide a composition that solves the above-mentioned problems, and a method for surface treatment of a wafer in which the vapor of the composition is used in the formation of a water-repellent protective film in the cleaning of wafers with Si elements . [Technical means to solve the problem]
本發明係一種晶圓之表面處理方法，其係於表面具有凹凸圖案，且至少於該凹部具有Si元素之晶圓(以後，有時簡記為「晶圓」)之洗淨中，於上述凹凸圖案之至少凹部保持有液體之狀態下，將含有撥水性保護膜形成成分與溶劑之組合物(以後，有時簡記為「組合物」)之蒸氣供給至上述凹凸圖案表面，使上述蒸氣之狀態變為液體狀態，將保持於上述凹部之液體置換為該組合物之液體，藉此至少於上述凹部表面形成撥水性保護膜(以後，有時簡記為「保護膜」)；且 上述撥水性保護膜形成成分僅為下述通式[1]所表示之化合物， 上述溶劑至少含有非環狀碳酸酯，溶劑總量中之上述非環狀碳酸酯之量為50～100質量%。 [化1] R1 x (CH3 )3-x SiN(R2 )2 [1] [式[1]中，R1 分別獨立為選自H基、碳數為1～10之烴基、及氫原子之一部分或全部被氟原子取代之碳數為1～10之烴基之基；x為1～3之整數；R2 分別相互獨立為選自氫原子之一部分或全部可被氟原子取代之甲基、乙基、乙醯基之基]。The present invention is a method for surface treatment of wafers, which has uneven patterns on the surface, and at least the recesses have Si elements in the cleaning of wafers (hereinafter, sometimes abbreviated as "wafer"), in the above-mentioned unevenness While at least the concave portion of the pattern is kept in a liquid state, the vapor of the composition (hereinafter, sometimes abbreviated as "composition") containing the water-repellent protective film forming component and the solvent is supplied to the surface of the uneven pattern to make the vapor state In a liquid state, the liquid held in the concave portion is replaced with the liquid of the composition, thereby forming a water-repellent protective film (hereinafter, sometimes abbreviated as "protective film") at least on the surface of the concave portion; and the water-repellent protection The film forming component is only the compound represented by the following general formula [1], the solvent contains at least acyclic carbonate, and the amount of the acyclic carbonate in the total solvent is 50 to 100% by mass. [Chemical Formula 1] R 1 x (CH 3 ) 3-x SiN(R 2 ) 2 [1] [In formula [1], R 1 is each independently selected from H groups, hydrocarbon groups having 1 to 10 carbon atoms, and A group of a hydrocarbon group of 1 to 10 carbons in which part or all of the hydrogen atoms are replaced by fluorine atoms; x is an integer of 1 to 3; R 2 is each independently selected from a part or all of hydrogen atoms that can be substituted by fluorine atoms The base of methyl, ethyl, acetyl].
重要的是溶劑總量中之上述非環狀碳酸酯之量為50～100質量%。若為50質量%以上，則難以產生由於加熱而於組合物中短時間內生成不溶物之現象，表現出化學穩定性。就化學穩定性之觀點而言，更佳為80～100質量%，特佳為90～100質量%，最佳為100質量%、即溶劑僅為非環狀碳酸酯。It is important that the amount of the acyclic carbonate in the total solvent is 50-100% by mass. If it is 50% by mass or more, it is difficult to generate insoluble matter in the composition in a short time due to heating, and it exhibits chemical stability. From the viewpoint of chemical stability, it is more preferably 80 to 100% by mass, particularly preferably 90 to 100% by mass, and most preferably 100% by mass, that is, the solvent is only acyclic carbonate.
於上述晶圓之表面處理方法中，上述通式[1]所表示之化合物較佳為選自由(CH3 )3 SiN(CH3 )2 、C2 H5 Si(CH3 )2 N(CH3 )2 、(C2 H5 )2 Si(CH3 )N(CH3 )2 、(C2 H5 )3 SiN(CH3 )2 、C3 H7 Si(CH3 )2 N(CH3 )2 、(C3 H7 )2 Si(CH3 )N(CH3 )2 、(C3 H7 )3 SiN(CH3 )2 、C4 H9 Si(CH3 )2 N(CH3 )2 、(C4 H9 )3 SiN(CH3 )2 、C5 H11 Si(CH3 )2 N(CH3 )2 、C6 H13 Si(CH3 )2 N(CH3 )2 、C7 H15 Si(CH3 )2 N(CH3 )2 、C8 H17 Si(CH3 )2 N(CH3 )2 、C9 H19 Si(CH3 )2 N(CH3 )2 、C10 H21 Si(CH3 )2 N(CH3 )2 、(CH3 )2 Si(H)N(CH3 )2 、CH3 Si(H)2 N(CH3 )2 、(C2 H5 )2 Si(H)N(CH3 )2 、C2 H5 Si(H)2 N(CH3 )2 、C2 H5 Si(CH3 )(H)N(CH3 )2 、(C3 H7 )2 Si(H)N(CH3 )2 、C3 H7 Si(H)2 N(CH3 )2 、CF3 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C2 F5 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C3 F7 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C4 F9 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C5 F11 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C6 F13 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C7 F15 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C8 F17 CH2 CH2 Si(CH3 )2 N(CH3 )2 、CF3 CH2 CH2 Si(CH3 )(H)N(CH3 )2 、上述二甲胺基矽烷之二甲胺基(-N(CH3 )2 基)為-N(C2 H5 )2 基之化合物、上述二甲胺基矽烷之二甲胺基為-N(CH3 )C(O)CH3 基之化合物、及上述二甲胺基矽烷之二甲胺基為-N(CH3 )C(O)CF3 基之化合物所組成之群之至少1種。In the above-mentioned wafer surface treatment method, the compound represented by the above-mentioned general formula [1] is preferably selected from (CH 3 ) 3 SiN(CH 3 ) 2 , C 2 H 5 Si(CH 3 ) 2 N(CH 3 ) 2 , (C 2 H 5 ) 2 Si(CH 3 )N(CH 3 ) 2 , (C 2 H 5 ) 3 SiN(CH 3 ) 2 , C 3 H 7 Si(CH 3 ) 2 N(CH 3 ) 2 , (C 3 H 7 ) 2 Si(CH 3 )N(CH 3 ) 2 , (C 3 H 7 ) 3 SiN(CH 3 ) 2 , C 4 H 9 Si(CH 3 ) 2 N(CH 3 ) 2 , (C 4 H 9 ) 3 SiN(CH 3 ) 2 , C 5 H 11 Si(CH 3 ) 2 N(CH 3 ) 2 , C 6 H 13 Si(CH 3 ) 2 N(CH 3 ) 2 , C 7 H 15 Si(CH 3 ) 2 N(CH 3 ) 2 , C 8 H 17 Si(CH 3 ) 2 N(CH 3 ) 2 , C 9 H 19 Si(CH 3 ) 2 N(CH 3 ) 2 , C 10 H 21 Si(CH 3 ) 2 N(CH 3 ) 2 , (CH 3 ) 2 Si(H)N(CH 3 ) 2 , CH 3 Si(H) 2 N(CH 3 ) 2 , (C 2 H 5 ) 2 Si(H)N(CH 3 ) 2 , C 2 H 5 Si(H) 2 N(CH 3 ) 2 , C 2 H 5 Si(CH 3 )(H)N(CH 3 ) 2 , (C 3 H 7 ) 2 Si(H)N(CH 3 ) 2 , C 3 H 7 Si(H) 2 N(CH 3 ) 2 , CF 3 CH 2 CH 2 Si(CH 3 ) 2 N (CH 3 ) 2 , C 2 F 5 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 3 F 7 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 4 F 9 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 5 F 11 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 6 F 13 CH 2 CH 2 Si( CH 3 ) 2 N(CH 3 ) 2 , C 7 F 15 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 8 F 17 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , CF 3 CH 2 CH 2 Si(CH 3 )(H)N(CH 3 ) 2 , the dimethylamine of the above-mentioned dimethylaminosilane Group (-N(CH 3 ) 2 group) is a compound of -N(C 2 H 5 ) 2 group, the dimethylamino group of the above-mentioned dimethylaminosilane is -N(CH 3 )C(O)CH 3 group At least one of the group consisting of the compound and the dimethylamino group of the above-mentioned dimethylaminosilane is -N(CH 3 )C(O)CF 3 group.
於上述晶圓之表面處理方法中，上述通式[1]所表示之化合物較佳為選自由三甲基矽烷基二甲基胺及三甲基矽烷基二乙基胺所組成之群之至少1種。In the above-mentioned wafer surface treatment method, the compound represented by the above-mentioned general formula [1] is preferably at least selected from the group consisting of trimethylsilyldimethylamine and
於上述晶圓之表面處理方法中，上述非環狀碳酸酯較佳為選自由碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯所組成之群之至少1種。In the surface treatment method of the wafer, the acyclic carbonate is preferably at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.
於上述晶圓之表面處理方法中，若上述通式[1]所表示之化合物之含量相對於上述組合物之總量為0.3質量%以上，則容易表現出充分之撥水性賦予效果，因此較佳，且若為30質量%以下，則就成本之觀點而言較佳。更佳為0.5～15質量%，進而較佳為1～10質量%。In the above-mentioned wafer surface treatment method, if the content of the compound represented by the above-mentioned general formula [1] is 0.3% by mass or more with respect to the total amount of the above-mentioned composition, it is easy to exhibit a sufficient water repellency imparting effect, and therefore it is more It is preferable, and if it is 30% by mass or less, it is preferable from the viewpoint of cost. It is more preferably 0.5 to 15% by mass, and still more preferably 1 to 10% by mass.
於上述晶圓之表面處理方法中，上述組合物之溶劑中之環狀碳酸酯之含量較佳為10質量%以下。In the above-mentioned wafer surface treatment method, the content of the cyclic carbonate in the solvent of the above-mentioned composition is preferably 10% by mass or less.
於上述晶圓之表面處理方法中，上述組合物較佳為僅由上述通式[1]所表示之化合物與上述非環狀碳酸酯所組成。In the above-mentioned wafer surface treatment method, the above-mentioned composition is preferably composed only of the compound represented by the above-mentioned general formula [1] and the above-mentioned acyclic carbonate.
於上述晶圓之表面處理方法中，保持於上述凹部之液體較佳為非水溶劑。In the surface treatment method of the wafer, the liquid held in the recess is preferably a non-aqueous solvent.
於上述晶圓之表面處理方法中，較佳為至少於上述凹部表面形成撥水性保護膜後，藉由乾燥而去除保持於該凹部之上述組合物。藉由該乾燥，去除上述組合物中之溶劑或與保護膜之形成無關的剩餘之通式[1]所表示之化合物等，從而於晶圓之凹部表面留下撥水性保護膜。In the surface treatment method of the wafer, it is preferable to remove the composition held in the concave portion by drying after forming a water-repellent protective film on at least the surface of the concave portion. By this drying, the solvent in the above composition or the remaining compound represented by the general formula [1] unrelated to the formation of the protective film is removed, thereby leaving a water-repellent protective film on the surface of the concave portion of the wafer.
於上述晶圓之表面處理方法中，較佳為至少於上述凹部表面形成撥水性保護膜後，將保持於該凹部之上述組合物之液體置換為與該組合物之液體不同之洗淨液，並藉由乾燥而去除該洗淨液。In the above-mentioned wafer surface treatment method, it is preferable that after forming a water-repellent protective film at least on the surface of the concave portion, the liquid of the composition held in the concave portion is replaced with a cleaning solution different from the liquid of the composition, And the washing liquid is removed by drying.
於上述晶圓之表面處理方法中，亦可對上述乾燥後之晶圓表面實施選自由加熱處理、光照射處理、臭氧暴露處理、電漿照射處理、及電暈放電處理所組成之群之至少1種處理而去除上述撥水性保護膜。In the above-mentioned wafer surface treatment method, the dried wafer surface can also be subjected to at least one selected from the group consisting of heat treatment, light irradiation treatment, ozone exposure treatment, plasma irradiation treatment, and corona discharge treatment. One type of treatment to remove the above-mentioned water-repellent protective film.
又，本發明係一種組合物，其係含有撥水性保護膜形成成分與溶劑者，且該組合物於表面具有凹凸圖案，且至少於該凹部具有Si元素之晶圓之洗淨中，於上述凹凸圖案之至少凹部保持有液體之狀態下，以蒸氣之形式供給至該凹凸圖案表面；且 上述撥水性保護膜形成成分僅為下述通式[1]所表示之化合物， 上述溶劑至少含有非環狀碳酸酯，溶劑總量中之上述非環狀碳酸酯之量為50～100質量%。 [化2] R1 x (CH3 )3-x SiN(R2 )2 [1] [式[1]中，R1 分別獨立為選自H基、碳數為1～10之烴基、及氫原子之一部分或全部被氟原子取代之碳數為1～10之烴基之基；x為1～3之整數；R2 分別相互獨立為選自氫原子之一部分或全部可被氟原子取代之甲基、乙基、乙醯基之基]。 [發明之效果]In addition, the present invention is a composition containing a water-repellent protective film forming component and a solvent, and the composition has a concave-convex pattern on the surface, and at least in the cleaning of a wafer with Si element in the concave portion, The concave-convex pattern is supplied to the surface of the concave-convex pattern in the form of a vapor while at least the concave portion of the concave-convex pattern is liquid; and the water-repellent protective film forming component is only the compound represented by the following general formula [1], and the solvent contains at least For the cyclic carbonate, the amount of the acyclic carbonate in the total solvent is 50-100% by mass. [Chemical 2] R 1 x (CH 3 ) 3-x SiN(R 2 ) 2 [1] [In formula [1], R 1 is each independently selected from H group, hydrocarbon group having 1 to 10 carbon atoms, and A group of a hydrocarbon group of 1 to 10 carbons in which part or all of the hydrogen atoms are replaced by fluorine atoms; x is an integer of 1 to 3; R 2 is each independently selected from a part or all of hydrogen atoms that can be substituted by fluorine atoms The base of methyl, ethyl, acetyl]. [Effects of Invention]
根據本發明，可提供撥水性保護膜形成成分之種類更少蒸氣處理用之新穎組合物，其可發揮與利用先前之(撥水性保護膜形成成分之種類較多之)組合物之蒸氣進行具有Si元素之晶圓表面之處理之情形同等之撥水性賦予效果，且化學穩定性優異；且可提供一種將上述新穎組合物之蒸氣用於撥水性保護膜之形成的具有Si元素之晶圓之表面處理方法。According to the present invention, a novel composition for steam treatment with fewer types of water-repellent protective film forming components can be provided. The surface treatment of the Si element of the wafer has the same effect of imparting water repellency and excellent chemical stability; and it can provide a wafer with Si element that uses the vapor of the above-mentioned novel composition for the formation of a water repellent protective film Surface treatment method.
(1)關於本發明之組合物 本發明之組合物係於表面具有凹凸圖案，且至少於該凹部具有Si元素之晶圓之洗淨中，於上述凹凸圖案之至少凹部保持有液體之狀態下，以蒸氣之形式供給至該凹凸圖案表面者，且該組合物係於上述凹部自蒸氣狀態變為液體狀態，並對原本保持於凹部之液體進行置換者。並且，藉由該置換使上述凹部保持有液體狀態之組合物，藉此於該凹部表面形成撥水性保護膜。(1) About the composition of the present invention The composition of the present invention has a concave-convex pattern on the surface, and is supplied to the concave-convex in the form of a vapor while at least the concave portion of the concave-convex pattern is kept in a liquid state during the cleaning of wafers with Si element in the concave portion. Those on the surface of the pattern, and the composition is changed from the vapor state to the liquid state in the recessed portion, and the liquid originally held in the recessed portion is replaced by the composition. And, by the replacement, the composition in the liquid state is maintained in the recessed portion, thereby forming a water-repellent protective film on the surface of the recessed portion.
就降低實際作用於晶圓表面之組成(於晶圓表面成為液體狀態之藥液組成)之不均之觀點而言，本發明之組合物之特徵在於撥水性保護膜形成成分之種類變少。又，該組合物係撥水性保護膜形成成分與溶劑之沸點越接近則越較佳。尤其是若上述組合物中所含有之通式[1]所表示之化合物(以後，有時記載為「矽烷化劑」)與非環狀碳酸酯此兩者之沸點差為50℃以內，則更容易降低上述之不均，因此較佳。From the viewpoint of reducing the unevenness of the composition actually acting on the wafer surface (the composition of the chemical solution that becomes liquid on the wafer surface), the composition of the present invention is characterized in that there are fewer types of water-repellent protective film forming components. In addition, the composition-based water-repellent protective film forming component and the solvent have a boiling point closer to each other, the better. In particular, if the boiling point difference between the compound represented by the general formula [1] (hereinafter, sometimes referred to as "silylation agent") contained in the above composition and the non-cyclic carbonate is within 50°C, then It is easier to reduce the above-mentioned unevenness, so it is preferable.
本發明者等經過潛心研究，結果發現上述通式[1]所表示之矽烷化劑作為即便是無觸媒(反應促進成分)之體系亦可發揮與專利文獻1所記載之藥液同等之撥水性賦予效果的撥水化劑。After intensive research, the inventors of the present invention found that the silylation agent represented by the general formula [1] can be used as a catalyst-free (reaction promoting component) system that is equivalent to the drug solution described in
於上述通式[1]所表示之矽烷化劑中，R1 x (CH3 )3-x Si係具有撥水性之官能基之部位。並且，藉由使含有氮原子之基與晶圓表面之矽烷醇基反應，上述具有撥水性之官能基之部位固定於晶圓表面，從而於該晶圓表面形成撥水性之保護膜。In the silylation agent represented by the general formula [1], R 1 x (CH 3 ) 3-x Si is a part having a water-repellent functional group. In addition, by reacting the nitrogen atom-containing group with the silanol group on the wafer surface, the portion having the water-repellent functional group is fixed on the wafer surface, thereby forming a water-repellent protective film on the wafer surface.
作為上述矽烷化劑之具體例，可列舉：(CH3 )3 SiN(CH3 )2 、C2 H5 Si(CH3 )2 N(CH3 )2 、(C2 H5 )2 Si(CH3 )N(CH3 )2 、(C2 H5 )3 SiN(CH3 )2 、C3 H7 Si(CH3 )2 N(CH3 )2 、(C3 H7 )2 Si(CH3 )N(CH3 )2 、(C3 H7 )3 SiN(CH3 )2 、C4 H9 Si(CH3 )2 N(CH3 )2 、(C4 H9 )3 SiN(CH3 )2 、C5 H11 Si(CH3 )2 N(CH3 )2 、C6 H13 Si(CH3 )2 N(CH3 )2 、C7 H15 Si(CH3 )2 N(CH3 )2 、C8 H17 Si(CH3 )2 N(CH3 )2 、C9 H19 Si(CH3 )2 N(CH3 )2 、C10 H21 Si(CH3 )2 N(CH3 )2 、(CH3 )2 Si(H)N(CH3 )2 、CH3 Si(H)2 N(CH3 )2 、(C2 H5 )2 Si(H)N(CH3 )2 、C2 H5 Si(H)2 N(CH3 )2 、C2 H5 Si(CH3 )(H)N(CH3 )2 、(C3 H7 )2 Si(H)N(CH3 )2 、C3 H7 Si(H)2 N(CH3 )2 、CF3 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C2 F5 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C3 F7 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C4 F9 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C5 F11 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C6 F13 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C7 F15 CH2 CH2 Si(CH3 )2 N(CH3 )2 、C8 F17 CH2 CH2 Si(CH3 )2 N(CH3 )2 、CF3 CH2 CH2 Si(CH3 )(H)N(CH3 )2 、或者上述二甲胺基矽烷之二甲胺基(-N(CH3 )2 基)為-N(C2 H5 )2 、-N(CH3 )C(O)CH3 、-N(CH3 )C(O)CF3 之化合物等。 其中，選自由三甲基矽烷基二甲基胺及三甲基矽烷基二乙基胺所組成之群之至少1種由於撥水性賦予效果更優異而較佳。As specific examples of the above-mentioned silylation agent, (CH 3 ) 3 SiN(CH 3 ) 2 , C 2 H 5 Si(CH 3 ) 2 N(CH 3 ) 2 , (C 2 H 5 ) 2 Si( CH 3 )N(CH 3 ) 2 , (C 2 H 5 ) 3 SiN(CH 3 ) 2 , C 3 H 7 Si(CH 3 ) 2 N(CH 3 ) 2 , (C 3 H 7 ) 2 Si( CH 3 )N(CH 3 ) 2 , (C 3 H 7 ) 3 SiN(CH 3 ) 2 , C 4 H 9 Si(CH 3 ) 2 N(CH 3 ) 2 , (C 4 H 9 ) 3 SiN( CH 3 ) 2 , C 5 H 11 Si(CH 3 ) 2 N(CH 3 ) 2 , C 6 H 13 Si(CH 3 ) 2 N(CH 3 ) 2 , C 7 H 15 Si(CH 3 ) 2 N (CH 3 ) 2 , C 8 H 17 Si(CH 3 ) 2 N(CH 3 ) 2 , C 9 H 19 Si(CH 3 ) 2 N(CH 3 ) 2 , C 10 H 21 Si(CH 3 ) 2 N(CH 3 ) 2 , (CH 3 ) 2 Si(H)N(CH 3 ) 2 , CH 3 Si(H) 2 N(CH 3 ) 2 , (C 2 H 5 ) 2 Si(H)N( CH 3 ) 2 , C 2 H 5 Si(H) 2 N(CH 3 ) 2 , C 2 H 5 Si(CH 3 )(H)N(CH 3 ) 2 , (C 3 H 7 ) 2 Si(H )N(CH 3 ) 2 , C 3 H 7 Si(H) 2 N(CH 3 ) 2 , CF 3 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 2 F 5 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 3 F 7 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 4 F 9 CH 2 CH 2 Si(CH 3 ) 2 N (CH 3 ) 2 , C 5 F 11 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 6 F 13 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 , C 7 F 15 CH 2 CH 2 Si(CH 3 ) 2 N(CH 3 ) 2 、C 8 F 17 CH 2 CH 2 Si (CH 3 ) 2 N(CH 3 ) 2 , CF 3 CH 2 CH 2 Si(CH 3 )(H)N(CH 3 ) 2 , or the dimethylamino group (-N(CH 3 ) 2 groups) are compounds of -N(C 2 H 5 ) 2 , -N(CH 3 )C(O)CH 3 , -N(CH 3 )C(O)CF 3 , etc. Among them, at least one selected from the group consisting of trimethylsilyl dimethyl amine and trimethyl silyl diethyl amine is preferable because it has a more excellent water repellency imparting effect.
上述非環狀碳酸酯係用於使上述通式[1]所表示之矽烷化劑溶解之溶劑成分。藉由使用如上所述之特定結構之矽烷化劑、與特定量之非環狀碳酸酯，從而使蒸氣化前之組合物中，矽烷化劑不易分解(組合物之化學穩定性較高)，且可對處理裝置內全體進行穩定之處理。The acyclic carbonate is a solvent component for dissolving the silylation agent represented by the general formula [1]. By using the above-mentioned specific structure of the silylation agent and a specific amount of acyclic carbonate, the silylation agent is not easily decomposed in the composition before vaporization (the composition has higher chemical stability). And it can perform stable processing on the entire processing device.
如專利文獻3及非專利文獻1所示，已知碳酸酯於加熱下與有機鹼反應。因此，預想到若使用碳酸酯作為本發明之組合物之溶劑成分，則於加熱時會消耗矽烷化劑，因此認為其並不適於蒸氣化。但是，意外的是並未發現矽烷化劑之明顯消耗，且明確了並未對撥水性賦予效果造成不良影響。其原因尚不詳細地明確，但認為其原因在於：通式[1]之矽烷化劑之氮原子上鍵結有體積較大之烷基矽烷基，因此由於立體阻礙而抑制反應。
又，若使用碳酸酯之1種的非環狀碳酸酯作為本發明之組合物之溶劑成分，則並未確認到由於與通式[1]之矽烷化劑之接觸而造成非環狀碳酸酯分解或變質，可知組合物之化學穩定性高。
另一方面，若使用作為碳酸酯之1種的環狀碳酸酯作為本發明之組合物之溶劑成分，則存在由於與通式[1]之矽烷化劑之接觸而檢測出生成被認為來自環狀碳酸酯之高沸點化合物之傾向，且存在該化合物隨著保管而增加之傾向。認為該現象係如非專利文獻1所示般由環狀碳酸酯之聚合物所生成者，基於此，就該組合物之化學穩定性之觀點而言，使該組合物含有較多之環狀碳酸酯作為組合物之溶劑此點欠佳。又，由於存在如下現象之虞而欠佳：該聚合物於蒸發時殘存於氣化器內；或者於晶圓表面，於自蒸氣變為液體狀態之藥液中，該聚合物作為不溶物而析出或沈澱。As shown in
本發明之組合物之溶劑成分亦可含有非環狀碳酸酯以外之有機溶劑，例如可列舉：丙酮、2-丁酮、4-甲基-2-戊酮、環己酮等酮；乙酸甲酯、乙酸乙酯、乙酸丁酯、丙二醇單甲醚乙酸酯等羧酸酯；碳酸乙二酯或碳酸丙二酯等環狀碳酸酯等，於其他溶劑係環狀碳酸酯之情形時，就組合物之化學穩定性之觀點、或用於表面處理之裝置或處理對象之晶圓之清潔性之觀點而言，組合物之溶劑中之該環狀碳酸酯之含量較佳為10質量%以下。就上述之觀點而言，更佳為於組合物中實質上不含環狀碳酸酯。 進而，就組合物之化學穩定性之觀點、或用於表面處理之裝置或處理對象之晶圓之清潔性之觀點而言，特佳為上述組合物係僅由上述矽烷化劑與上述非環狀碳酸酯所組成者。The solvent component of the composition of the present invention may also contain organic solvents other than acyclic carbonate, for example, ketones such as acetone, 2-butanone, 4-methyl-2-pentanone, and cyclohexanone; methyl acetate Ester, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and other carboxylic acid esters; cyclic carbonates such as ethylene carbonate or propylene carbonate, etc., when other solvents are cyclic carbonates, From the viewpoint of the chemical stability of the composition, or the viewpoint of the cleanability of the device used for surface treatment or the wafer to be processed, the content of the cyclic carbonate in the solvent of the composition is preferably 10% by mass the following. From the above viewpoint, it is more preferable that the cyclic carbonate is not substantially contained in the composition. Furthermore, from the viewpoint of the chemical stability of the composition, or the viewpoint of the cleanability of the device used for surface treatment or the wafer to be processed, it is particularly preferred that the composition is composed of the above-mentioned silylation agent and the above-mentioned acyclic Formed by carbonic acid esters.
作為上述非環狀碳酸酯，例如可列舉：碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸二正丙酯、碳酸二異丙酯、碳酸二正丁酯、碳酸二正己酯、碳酸二(3-甲氧基丙基)酯等，其中選自由碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯所組成之群之至少1種與矽烷化劑之混合性高而較佳。Examples of the aforementioned acyclic carbonate include: dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, di-n-hexyl carbonate, Bis(3-methoxypropyl) carbonate, etc., among which at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate has high mixing properties with a silylation agent and is preferred .
又，上述組合物之起始原料中之水分之總量相對於該原料之總量較佳為2000質量ppm以下。於水分量之總量超過2000質量ppm之情形時，上述矽烷化劑之效果降低，變得難以短時間內形成上述保護膜。因此，上述組合物原料中之水分量之總量越少則越佳，特佳為500質量ppm以下，進而較佳為200質量ppm以下。進而，若水之存在量較多，則上述組合物之保管穩定性易降低，因此較佳為水分量少，較佳為100質量ppm以下，進而較佳為50質量ppm以下。再者，雖然上述水分量越少則越佳，但如果是上述之含量範圍內，則上述組合物原料中之水分量可為0.1質量ppm以上。因此，較佳為上述組合物所含有之矽烷化劑或溶劑並不含有較多之水。In addition, the total amount of moisture in the starting material of the above composition is preferably 2000 ppm by mass or less with respect to the total amount of the material. When the total amount of water exceeds 2000 ppm by mass, the effect of the above-mentioned silylation agent decreases, and it becomes difficult to form the above-mentioned protective film in a short time. Therefore, the smaller the total amount of water in the composition raw material, the better, and it is particularly preferably 500 ppm by mass or less, and more preferably 200 ppm by mass or less. Furthermore, if the amount of water present is large, the storage stability of the composition is likely to decrease. Therefore, the water content is preferably small, preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less. Furthermore, although the smaller the amount of the above-mentioned water, the better, but if it is within the above-mentioned content range, the amount of water in the above-mentioned composition raw material may be 0.1 mass ppm or more. Therefore, it is preferable that the silylation agent or solvent contained in the above composition does not contain much water.
又，上述組合物中之液相中之利用光散射式液中粒子檢測器而測定微粒時之大於0.2 μm之粒子數較佳為每1 mL該組合物中為100個以下。若上述大於0.2 μm之粒子數為每1 mL該組合物中超過100個，則存在由於微粒而誘發圖案損壞之虞，且成為引起裝置之良率降低及可靠性降低之原因，因此欠佳。又，蒸氣處理裝置內受到污染，裝置之良率降低及可靠性降低會持續化。又，若大於0.2 μm之粒子數為每1 mL該組合物中為100個以下，則可省略或減少形成上述保護膜後之利用溶劑或水對該晶圓表面(保護膜表面)進行洗淨之操作，因此較佳。再者，雖然上述大於0.2 μm之粒子之數越少則越佳，但如果是上述含量範圍內，則可為每1 mL該組合物中為1個以上。再者，該組合物中之液相中之微粒測定係利用將雷射作為光源之光散射式液中粒子測定方式之市售之測定裝置而測定者，且所謂微粒之粒徑係指PSL(Polystyrene latex，聚苯乙烯製乳膠)標準粒子基準之光散射當量徑。In addition, the number of particles larger than 0.2 μm in the liquid phase of the above-mentioned composition is preferably 100 or less per 1 mL of the composition when using a light scattering type in-liquid particle detector to measure particles. If the number of particles larger than 0.2 μm is more than 100 per 1 mL of the composition, there is a risk of pattern damage induced by the particles, which may cause a decrease in the yield and reliability of the device, which is not good. In addition, if the steam treatment device is contaminated, the yield rate and reliability of the device will continue to decrease. In addition, if the number of particles larger than 0.2 μm is less than 100 per 1 mL of the composition, it is possible to omit or reduce the use of solvent or water to clean the wafer surface (protective film surface) after forming the protective film. The operation is therefore better. Furthermore, although the number of particles larger than 0.2 μm described above is preferably as small as possible, if it is within the above content range, it may be 1 or more per 1 mL of the composition. Furthermore, the measurement of particles in the liquid phase in the composition is measured by a commercially available measuring device using a light-scattering method of measuring particles in the liquid using a laser as a light source, and the so-called particle size refers to PSL ( Polystyrene latex (polystyrene latex) standard particle standard light scattering equivalent diameter.
此處，上述所謂微粒相當於作為雜質而含有於原料中之塵埃、灰塵、有機固形物、無機固形物等之粒子、或於組合物之製備中作為污染物被帶入之塵埃、灰塵、有機固形物、無機固形物等之粒子等，且最終於組合物中未溶解而以粒子之形式存在者。Here, the above-mentioned so-called fine particles correspond to particles such as dust, dust, organic solids, inorganic solids, etc. contained in the raw materials as impurities, or dust, dust, organic particles that are brought in as pollutants during the preparation of the composition. Particles of solids, inorganic solids, etc., which are not dissolved in the composition but exist in the form of particles.
又，上述組合物中之Na、Mg、K、Ca、Mn、Fe、Cu、Li、Al、Cr、Ni、Zn及Ag之各元素(金屬雜質)之含量相對於該組合物總量而言較佳為各0.1質量ppb以下。若上述金屬雜質之含量相對於該組合物總量超過0.1質量ppb，則存在使裝置之接合漏電流增大之虞，且成為引起裝置之良率降低及可靠性降低之原因，因此欠佳。又，蒸氣處理裝置內受到污染，裝置之良率降低及可靠性降低會持續化。又，若上述金屬雜質之含量相對於該組合物總量為0.1質量ppb以下，則可省略或減少於晶圓表面形成上述保護膜後之利用溶劑或水對該晶圓表面(保護膜表面)進行洗淨之操作，因此較佳。因此，雖然上述金屬雜質之含量越少則越佳，但如果是上述之含量範圍內，則相對於該組合物之總量而言，各元素可為0.001質量ppb以上。In addition, the content of each element (metal impurity) of Na, Mg, K, Ca, Mn, Fe, Cu, Li, Al, Cr, Ni, Zn, and Ag in the above composition is relative to the total amount of the composition Preferably, each is 0.1 mass ppb or less. If the content of the metal impurities exceeds 0.1 mass ppb with respect to the total amount of the composition, there is a possibility that the junction leakage current of the device will increase, and it will cause a decrease in the yield and reliability of the device, so it is not good. In addition, if the steam treatment device is contaminated, the yield rate and reliability of the device will continue to decrease. In addition, if the content of the metal impurities is less than 0.1 mass ppb relative to the total composition of the composition, the use of solvent or water on the wafer surface (protective film surface) after the protective film is formed on the wafer surface can be omitted or reduced. It is better to perform washing operation. Therefore, although the content of the above-mentioned metal impurities is less, the better, but if it is within the above-mentioned content range, each element can be 0.001 mass ppb or more relative to the total amount of the composition.
(2)關於撥水性保護膜 本發明之表面處理方法及組合物中，所謂撥水性保護膜係指藉由形成於晶圓表面而降低該晶圓表面之潤濕性之膜，即賦予撥水性之膜。本發明之表面處理方法及組合物中，所謂撥水性係指使物品表面之表面能量降低，從而使水或其他液體與該物品表面之間(界面)之相互作用，例如氫鍵、分子間力等降低。尤其是對於水而言，使相互作用降低之效果較大，但對於水與水以外之液體之混合液、或水以外之液體而言，亦具有使相互作用降低之效果。藉由該相互作用之降低，可增大液體相對於物品表面之接觸角。再者，撥水性保護膜可為由上述矽烷化劑所形成者，亦可為含有以矽烷化劑為主成分之反應物者。(2) About water-repellent protective film In the surface treatment method and composition of the present invention, the so-called water-repellent protective film refers to a film that reduces the wettability of the wafer surface by being formed on the surface of the wafer, that is, a film that imparts water-repellency. In the surface treatment method and composition of the present invention, the so-called water repellency refers to reducing the surface energy of the article surface, thereby enabling the interaction between water or other liquids and the article surface (interface), such as hydrogen bonds, intermolecular forces, etc. reduce. Especially for water, the effect of reducing the interaction is great, but for a mixture of water and a liquid other than water, or a liquid other than water, it also has the effect of reducing the interaction. By reducing the interaction, the contact angle of the liquid relative to the surface of the article can be increased. Furthermore, the water-repellent protective film may be formed of the above-mentioned silylation agent, or may be one that contains a reactant whose main component is the silylation agent.
(3)關於晶圓 作為上述之晶圓，包括：於晶圓表面形成有矽、氧化矽、或氮化矽等含有Si元素之膜者；或者形成上述凹凸圖案時，該凹凸圖案之表面之至少一部分含有矽、氧化矽、或氮化矽等含有Si元素者。再者，可藉由上述組合物而形成保護膜的是於上述凹凸圖案中之含有Si元素之部分之表面。(3) About wafer The above-mentioned wafer includes: a film containing Si element such as silicon, silicon oxide, or silicon nitride is formed on the surface of the wafer; or when the above-mentioned uneven pattern is formed, at least a part of the surface of the uneven pattern contains silicon, oxide Silicon or silicon nitride containing Si element. Furthermore, the protective film can be formed from the above-mentioned composition on the surface of the portion containing the Si element in the above-mentioned concavo-convex pattern.
一般情況下，為了獲得表面具有微細之凹凸圖案之晶圓，首先，於平滑之晶圓表面塗佈抗蝕劑，然後經由抗蝕劑遮罩對抗蝕劑進行曝光，將進行了曝光之抗蝕劑、或未進行曝光之抗蝕劑蝕刻去除，藉此製作具有所需凹凸圖案之抗蝕劑。又，亦可藉由將具有圖案之模具壓抵於抗蝕劑上而獲得具有凹凸圖案之抗蝕劑。其次，對晶圓進行蝕刻。此時，選擇性地蝕刻與抗蝕劑圖案之凹起部分對應之晶圓表面。最後，剝離抗蝕劑，獲得具有微細之凹凸圖案之晶圓。Generally, in order to obtain a wafer with a fine concave-convex pattern on the surface, first, a resist is coated on the smooth surface of the wafer, and then the resist is exposed through a resist mask, and the exposed resist The resist, or the unexposed resist is etched and removed, thereby making a resist with the desired concave-convex pattern. In addition, a resist with a concave-convex pattern can also be obtained by pressing a mold with a pattern against the resist. Second, the wafer is etched. At this time, the surface of the wafer corresponding to the concave portion of the resist pattern is selectively etched. Finally, the resist is stripped to obtain a wafer with a fine uneven pattern.
將上述晶圓表面製成具有微細之凹凸圖案之面後，利用水系洗淨液進行表面之洗淨，藉由乾燥等去除水系洗淨液，若凹部之寬度較小，凸部之縱橫比較大，則變得易發生圖案崩塌。該凹凸圖案如圖1及圖2所記載那樣進行定義。圖1係表示對表面為具有微細之凹凸圖案2之面的晶圓1進行斜視時之模式圖，圖2係表示圖1中之a-a'剖面之一部分者。凹部之寬度5如圖2所示那樣以相鄰之凸部3與凸部3之間隔進行表示，凸部之縱橫比係以凸部之高度6除以凸部之寬度7而所得者表示。於凹部之寬度為70 nm以下，尤其是45 nm以下，縱橫比為4以上，尤其是6以上時，變得容易產生洗淨步驟中之圖案崩塌。
再者，作為本發明之組合物及表面處理方法之處理對象，並不限定於上述之結構之晶圓，例如亦可將三維結構之半導體晶圓作為對象。After forming the surface of the wafer with a fine uneven pattern, the surface is cleaned with a water-based cleaning solution, and the water-based cleaning solution is removed by drying. If the width of the concave portion is small, the aspect ratio of the convex portion is larger , It becomes prone to pattern collapse. The concavo-convex pattern is defined as described in FIGS. 1 and 2. FIG. 1 is a schematic diagram of a
(4)關於晶圓之表面處理方法 至於如上所述地藉由蝕刻而獲得之表面具有微細之凹凸圖案之晶圓，為了於本發明之表面處理方法之前將蝕刻之殘渣等去除，可藉由水系洗淨液進行洗淨，亦可於該洗淨後將保持於凹部之水系洗淨液置換為與該水系洗淨液不同之洗淨液(以後，記載為「洗淨液A」)後進一步進行洗淨。(4) About the surface treatment method of the wafer As for the wafers with fine concavo-convex patterns on the surface obtained by etching as described above, in order to remove the etching residues and the like before the surface treatment method of the present invention, it can be cleaned with an aqueous cleaning solution or After the washing, the water-based cleaning solution held in the recessed portion is replaced with a cleaning solution different from the water-based cleaning solution (hereinafter, referred to as "washing solution A"), and then further washing is performed.
作為上述水系洗淨液之例，可列舉水、或者於水中混合有機溶劑、過氧化氫、臭氧、酸、鹼、界面活性劑中之至少1種的水溶液(例如，水之含有率為10質量%以上)。As an example of the above-mentioned water-based cleaning solution, water, or an aqueous solution of at least one of organic solvents, hydrogen peroxide, ozone, acid, alkali, and surfactant mixed with water (for example, the water content rate is 10 mass %above).
又，所謂上述洗淨液A係表示有機溶劑、該有機溶劑與水系洗淨液之混合物、於其等中混合有酸、鹼、界面活性劑中之至少1種的洗淨液。In addition, the above-mentioned cleaning liquid A refers to an organic solvent, a mixture of the organic solvent and an aqueous cleaning liquid, a cleaning liquid in which at least one of an acid, an alkali, and a surfactant is mixed therein.
作為於晶圓之凹凸圖案之至少凹部保持上述水系洗淨液或洗淨液A之方式，可列舉：單片方式，其以使用如下之旋轉洗淨裝置的洗淨方法為代表，上述旋轉洗淨裝置一面使晶圓大致保持水平而進行旋轉，一面於旋轉中心附近供給液體，逐片地對晶圓進行洗淨；或分批方式，其使用於洗淨槽內浸漬複數片之晶圓而進行洗淨之洗淨裝置。As a method of holding the above-mentioned water-based cleaning solution or cleaning solution A in at least the concave portion of the concave-convex pattern of the wafer, there can be mentioned: a single-chip method, which is represented by a cleaning method using the following rotary cleaning device, the above-mentioned rotary cleaning The cleaning device rotates the wafer while keeping the wafer roughly horizontal, while supplying liquid near the center of rotation to clean the wafers one by one; or a batch method, which is used to immerse a plurality of wafers in the cleaning tank. Washing device for washing.
關於作為上述洗淨液A之較佳例之一的有機溶劑之例，可列舉：烴類、酯類、醚類、酮類、含鹵素溶劑、亞碸系溶劑、內酯系溶劑、碳酸酯系溶劑、醇類、多元醇之衍生物、含有氮元素之溶劑等。Regarding examples of organic solvents as one of the preferred examples of the above-mentioned cleaning solution A, hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfite-based solvents, lactone-based solvents, and carbonates can be cited. Series solvents, alcohols, polyol derivatives, solvents containing nitrogen, etc.
於凹凸圖案之至少凹部保持有上述水系洗淨液或洗淨液A等液體之狀態下，將本發明之組合物之蒸氣供給至上述凹凸圖案表面，於晶圓表面使該蒸氣狀態變為上述組合物之液體狀態，將保持於上述凹部之液體置換為該組合物之液體並保持，藉此至少於上述凹部表面形成撥水性保護膜。 於本發明之表面處理方法中，作為將組合物之蒸氣供給至上述凹凸圖案表面之方法，例如可列舉：於腔室內配置於凹凸圖案之至少凹部保持有上述液體之晶圓，將另行使組合物蒸發而獲得之蒸氣經由配管或噴嘴供給至凹凸圖案表面之方法等。於供給蒸氣時亦可使用氮氣或乾燥空氣等載氣。In a state where at least the concave portion of the concave-convex pattern holds the above-mentioned water-based cleaning solution or cleaning solution A, the vapor of the composition of the present invention is supplied to the surface of the concave-convex pattern, and the vapor state is changed to the above-mentioned state on the wafer surface In the liquid state of the composition, the liquid held in the concave portion is replaced with the liquid of the composition and maintained, thereby forming a water-repellent protective film at least on the surface of the concave portion. In the surface treatment method of the present invention, as a method of supplying vapor of the composition to the surface of the concave-convex pattern, for example, a wafer with the liquid held in at least the concave portion of the concave-convex pattern is arranged in a chamber and combined separately A method in which the vapor obtained by evaporation of the substance is supplied to the surface of the concave-convex pattern through a pipe or a nozzle. Carrier gas such as nitrogen or dry air can also be used when supplying steam.
又，上述之被置換保持之液體狀態之組合物亦可被置換為與該組合物不同之洗淨液(以後，記載為「洗淨液B」)。In addition, the above-mentioned composition in a liquid state that is replaced and maintained may be replaced with a cleaning solution different from the composition (hereinafter referred to as "cleaning solution B").
如上所述地利用水系洗淨液或洗淨液A進行洗淨之後，使用蒸氣將該洗淨液置換為液體狀態之組合物，於凹凸圖案之至少凹部保持有液體狀態之該組合物之過程中，於該凹凸圖案之至少凹部表面形成上述保護膜。藉由本發明之方法而形成之保護膜可以不必連續地形成，又，亦可不必均勻地形成，但為了可賦予更優異之撥水性，更佳為連續且均勻地形成。After washing with water-based detergent or detergent A as described above, the process of replacing the detergent with a composition in a liquid state with steam, and maintaining the composition in a liquid state in at least the recesses of the concave-convex pattern In this case, the protective film is formed on at least the surface of the concave portion of the concave-convex pattern. The protective film formed by the method of the present invention may not be formed continuously or evenly, but in order to provide more excellent water repellency, it is more preferably formed continuously and uniformly.
圖3表示向保持有洗淨液等液體8之凹部供給組合物之蒸氣9之狀態之模式圖。圖3之模式圖之晶圓係表示圖1之a-a'剖面之一部分者。所供給之蒸氣於凹部狀態變為液體狀態，將原本保持於凹部之液體8置換為該組合物之液體，於上述凹部保持液體狀態之組合物。使所保持之組合物中之上述矽烷化劑與晶圓表面之矽烷醇基反應，將上述具有撥水性之官能基之部位固定於晶圓表面，藉此於該凹部表面形成撥水性保護膜。Fig. 3 is a schematic diagram showing a state in which the
使本發明之組合物蒸氣化之方法無特別限定。 例如，可列舉分批式之蒸氣化方法，即，將特定量之液體狀態之組合物導入至氣化室，進行充分之加熱以使該組合物全部蒸發，於全部蒸發後，為了將該蒸氣供給至上述凹凸圖案表面而將其送至配管或噴嘴。 又，例如，可列舉連續式之蒸氣化方法，即，於預先進行了加熱之小規模之氣化部(例如，於配管之一部分設置加熱機構等)滴加組合物之液滴，以使每次滴加組合物全部蒸發之方式進行滴加，且為了將該蒸氣供給至上述凹凸圖案表面而將其送至配管或噴嘴。 再者，較佳為將蒸氣化之溫度抑制為並無引起作為保護膜形成成分之上述矽烷化劑熱分解之虞的溫度。 作為較佳之蒸氣處理之條件，可列舉：導入氮氣，於如上所述而獲得之蒸氣與該氮氣之混合氣體之組成變固定之後，向上述凹凸圖案表面供給該混合氣體。較佳為處理中之基板附近之氣氛溫度、即蒸氣之溫度低於原本保持於凹部之液體之沸點。其原因在於：若氣氛溫度(蒸氣之溫度)為該沸點以上，則存在如下之虞，即，於將原本保持於凹部之液體藉由蒸氣處理充分地置換為液體狀態之上述組合物之前，保持於凹部之該液體揮發，從而使該凹凸圖案崩塌。The method of vaporizing the composition of the present invention is not particularly limited. For example, a batch-type vaporization method can be cited, that is, a specific amount of a composition in a liquid state is introduced into a vaporization chamber, and sufficient heating is performed to evaporate the composition. It is supplied to the surface of the above-mentioned concavo-convex pattern and sent to a pipe or a nozzle. In addition, for example, a continuous vaporization method can be cited, that is, a small-scale vaporization section that has been heated in advance (for example, a heating mechanism is provided in a part of a pipe) droplets of the composition so that each The composition is dripped so that all of the composition for the secondary dripping is evaporated, and the vapor is sent to a pipe or a nozzle in order to supply the vapor to the surface of the above-mentioned concave-convex pattern. Furthermore, it is preferable to suppress the vaporization temperature to a temperature that does not cause the thermal decomposition of the silylation agent as a protective film forming component. As a preferable condition of the steam treatment, it is possible to include: introducing nitrogen gas, and supplying the mixed gas to the surface of the concave-convex pattern after the composition of the mixed gas of the steam and the nitrogen obtained as described above becomes fixed. Preferably, the temperature of the atmosphere near the substrate being processed, that is, the temperature of the vapor, is lower than the boiling point of the liquid originally held in the recess. The reason is that if the atmospheric temperature (temperature of the vapor) is higher than the boiling point, there is a possibility that the liquid originally held in the recessed portion is sufficiently replaced by the vapor treatment to the above-mentioned composition in the liquid state. The liquid in the concave portion volatilizes, so that the concave-convex pattern collapses.
亦可如上所述地形成保護膜後，於將殘留於凹凸圖案之至少凹部之液體狀態之上述組合物置換為洗淨液B後，移行至乾燥步驟。After the protective film is formed as described above, the liquid composition remaining in at least the concave portion of the concavo-convex pattern may be replaced with the cleaning solution B, and then proceed to the drying step.
作為該洗淨液B之例，可列舉：水系洗淨液、有機溶劑、水系洗淨液與有機溶劑之混合物、或於其等中混合有酸、鹼、界面活性劑中之至少1種者、以及其等與上述組合物之混合物等。就去除微粒或金屬雜質之觀點而言，上述洗淨液B更佳為水、有機溶劑、或水與有機溶劑之混合物。Examples of the cleaning solution B include: an aqueous cleaning solution, an organic solvent, a mixture of an aqueous cleaning solution and an organic solvent, or a mixture of at least one of an acid, an alkali, and a surfactant , And mixtures thereof and the above-mentioned compositions. From the viewpoint of removing particles or metal impurities, the above-mentioned cleaning solution B is more preferably water, an organic solvent, or a mixture of water and an organic solvent.
洗淨液B之供給可為以液體之方式供給該洗淨液之方法，亦可為以蒸氣之方式供給該洗淨液之方法。The supply of the cleaning solution B may be a method of supplying the cleaning solution in a liquid manner, or a method of supplying the cleaning solution in a vapor manner.
關於作為上述洗淨液B之較佳例之一的有機溶劑之例，可列舉：烴類、酯類、醚類、酮類、含鹵素溶劑、亞碸系溶劑、內酯系溶劑、碳酸酯系溶劑、醇類、多元醇之衍生物、含有氮元素之溶劑等。其中，為了廉價地獲得微粒或金屬雜質較少之品質者，較佳為異丙醇。Examples of organic solvents as one of the preferred examples of the cleaning solution B include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfite-based solvents, lactone-based solvents, and carbonates. Series solvents, alcohols, polyol derivatives, solvents containing nitrogen, etc. Among them, in order to obtain quality with less fine particles or metal impurities inexpensively, isopropyl alcohol is preferred.
又，上述保護膜若使用有機溶劑作為上述洗淨液B，則存在不易由於該洗淨液B之洗淨而造成撥水性降低之情形。In addition, if the protective film uses an organic solvent as the cleaning solution B, it is unlikely that the water repellency will decrease due to the cleaning of the cleaning solution B.
於藉由本發明之組合物而撥水化之凹部4保持有液體之情形之模式圖如圖4所示。圖4之模式圖之晶圓係表示圖1之a-a'剖面之一部分者。凹凸圖案表面係藉由上述組合物形成保護膜11而被撥水化。而且，該保護膜11於將液體10自凹凸圖案去除時亦保持於晶圓表面。Fig. 4 shows a schematic diagram of the case where the recessed
藉由本發明之組合物於晶圓之凹凸圖案之至少凹部表面形成保護膜11時，若假定於該表面保持有水時之接觸角為70～130°，則不易發生圖案崩塌，因此較佳。若接觸角較大則撥水性優異，因此接觸角更佳為75～130°，特佳為80～130°。又，於利用洗淨液B進行洗淨之前後，上述接觸角之降低量(洗淨液B之洗淨前之接觸角－洗淨液B之洗淨後之接觸角)較佳為10°以下。When the
其次，藉由乾燥將保持於藉由上述組合物而形成有保護膜之凹部4之液體自凹凸圖案中去除。此時，保持於凹部之液體可為液體狀態之上述組合物、上述洗淨液B、或其等之混合液。上述混合液係以組合物中所含有之各成分(矽烷化劑)較該組合物而言為低濃度之方式而含有者，且該混合液可為將液體狀態之上述組合物置換為洗淨液B之中途狀態之液體，亦可為預先將上述各成分混合於洗淨液B中而獲得之混合液。就晶圓之清潔度之觀點而言，較佳為水、有機溶劑、或水與有機溶劑之混合物。又，亦可暫時自上述凹凸圖案表面去除液體後，使洗淨液B保持於上述凹凸圖案表面，其後進行乾燥。Next, the liquid held in the
再者，於形成保護膜後利用洗淨液B進行洗淨時，就上述凹凸圖案表面之微粒或金屬雜質之去除之觀點而言，該洗淨之時間、即洗淨液B所保持之時間較佳為進行10秒以上，更佳為進行20秒以上。就形成於上述凹凸圖案表面之保護膜的撥水性能維持效果之觀點而言，若使用有機溶劑作為洗淨液B，則存在即便進行該洗淨也容易維持晶圓表面之撥水性之傾向。另一方面，若上述洗淨之時間變得過長，則生產性變差，因此較佳為15分鐘以內。Furthermore, when cleaning with the cleaning solution B after the protective film is formed, from the viewpoint of the removal of particles or metal impurities on the surface of the concave-convex pattern, the cleaning time, that is, the time that the cleaning solution B keeps It is preferably carried out for 10 seconds or more, and more preferably for 20 seconds or more. From the viewpoint of the water repellency maintenance effect of the protective film formed on the surface of the concave-convex pattern, if an organic solvent is used as the cleaning solution B, there is a tendency that the water repellency of the wafer surface is easily maintained even if the cleaning is performed. On the other hand, if the washing time becomes too long, the productivity deteriorates, so it is preferably within 15 minutes.
藉由上述乾燥而去除保持於凹凸圖案之液體。該乾燥較佳為利用旋轉乾燥法、IPA(2-丙醇)蒸氣乾燥、馬蘭葛尼乾燥、加熱乾燥、熱風乾燥、送風乾燥、真空乾燥等周知之乾燥方法而進行。The liquid held in the concave-convex pattern is removed by the above-mentioned drying. This drying is preferably performed by a known drying method such as spin drying, IPA (2-propanol) steam drying, Marangoni drying, heat drying, hot air drying, air blowing drying, and vacuum drying.
亦可於上述乾燥後進而去除保護膜11。於去除撥水性保護膜之情形時，有效的是切斷該撥水性保護膜中之C-C鍵、C-F鍵之方法。作為該方法，只要是可切斷上述鍵之方法就沒有特別限定，例如可列舉：對晶圓表面進行光照射之方法、對晶圓進行加熱之方法、對晶圓進行臭氧暴露之方法、對晶圓表面照射電漿之方法、對晶圓表面進行電暈放電之方法等。The
於藉由光照射去除保護膜11之情形時，較佳為照射紫外線，該紫外線包含比355 nm、340 nm、240 nm更短之波長，上述波長之能量相當於該保護膜11中之C-Si鍵、C-C鍵、C-F鍵之鍵結能量336 kJ/mol、347 kJ/mol、485 kJ/mol。該光源使用金屬鹵素燈、低壓水銀燈、高壓水銀燈、準分子燈、碳弧等。至於紫外線照射強度，若為金屬鹵素燈，則例如照度計(Konica Minolta Sensing製造之照射強度計UM-10，受光部UM-360[峰值感度波長：365 nm，測定波長範圍：310～400 nm])之測定值較佳為100 mW/cm2
以上，特佳為200 mW/cm2
以上。再者，若照射強度未達100 mW/cm2
，則變得需要較長時間以去除保護膜11。又，若為低壓水銀燈，則變為照射更短波長之紫外線，從而即便照射強度較低，亦可短時間內去除保護膜11，因此較佳。When the
又，於藉由光照射去除保護膜11之情形時，若藉由紫外線分解保護膜11之構成成分之同時產生臭氧，藉由該臭氧使保護膜11之構成成分氧化揮發，則處理時間變短，因此尤佳。該光源使用低壓水銀燈或準分子燈等。又，亦可一面進行光照射，一面對晶圓進行加熱。In addition, when the
於對晶圓進行加熱之情形時，於400～1000℃、較佳為500～900℃下進行晶圓之加熱。較佳為該加熱時間保持10秒～60分鐘，更佳為保持30秒～10分鐘。又，於該步驟中，亦可併用臭氧暴露、電漿照射、電暈放電等。又，亦可一面對晶圓進行加熱，一面進行光照射。In the case of heating the wafer, the wafer is heated at 400-1000°C, preferably 500-900°C. Preferably, the heating time is maintained for 10 seconds to 60 minutes, and more preferably, the heating time is maintained for 30 seconds to 10 minutes. In addition, in this step, ozone exposure, plasma irradiation, corona discharge, etc. may be used in combination. In addition, it is also possible to heat the wafer while irradiating light.
藉由加熱去除保護膜11之方法有：使晶圓與熱源接觸之方法、將晶圓放置於熱處理爐等進行了加熱之氣氛中之方法等。再者，將晶圓放置於進行了加熱之氣氛中之方法即便在對複數片晶圓進行處理之情形時，亦容易向晶圓表面均勻地賦予用於去除保護膜11之能量，因此其係操作簡便且可短時間內完成處理的處理能力高的對於工業性有利之方法。Methods of removing the
於對晶圓進行臭氧暴露之情形時，較佳為將藉由利用低壓水銀燈等之紫外線照射或利用高電壓之低溫放電等而產生之臭氧供給至晶圓表面。可一面對晶圓進行臭氧暴露一面進行光照射，亦可一面對晶圓進行臭氧暴露一面進行加熱。When the wafer is exposed to ozone, it is preferable to supply ozone generated by ultraviolet irradiation using a low-pressure mercury lamp or the like, or by using high-voltage low-temperature discharge, etc., to the surface of the wafer. The ozone-exposed side of the wafer can be irradiated with light, or the ozone-exposed side of the wafer can be heated.
可藉由將上述之光照射、加熱、臭氧暴露、電漿照射、電暈放電加以組合而有效率地去除晶圓表面之保護膜。 實施例The protective film on the wafer surface can be efficiently removed by combining the above-mentioned light irradiation, heating, ozone exposure, plasma irradiation, and corona discharge. Example
以下，表示更具體地揭示本發明之實施形態之實施例。再者，本發明並不僅限於該等實施例。Hereinafter, there will be shown an example that more specifically discloses the embodiment of the present invention. Furthermore, the present invention is not limited to these embodiments.
至於將晶圓之表面製成具有凹凸圖案之面、以及將保持於凹凸圖案之至少凹部的洗淨液置換為其他洗淨液，於其他文獻等中也進行了各種研究，係已確定之技術，因此於本發明中，對組合物之化學穩定性、與藉由該組合物之蒸氣對晶圓進行表面處理時之撥水性賦予效果進行評價。再者，於實施例中，作為評價接觸角時與晶圓表面接觸之液體，使用水系洗淨液之代表性物質，即水。As for making the surface of the wafer a surface with a concave-convex pattern, and replacing the cleaning solution held in at least the concave portion of the concave-convex pattern with another cleaning solution, various studies have also been conducted in other documents, and it is an established technology. Therefore, in the present invention, the chemical stability of the composition and the effect of imparting water repellency when the wafer is surface treated by the vapor of the composition are evaluated. Furthermore, in the examples, as the liquid that comes into contact with the wafer surface when evaluating the contact angle, water, which is a representative substance of the water-based cleaning liquid, is used.
但是，於表面具有凹凸圖案之晶圓之情形時，無法對形成於該凹凸圖案表面之上述保護膜11自身之接觸角正確地進行評價。However, in the case of a wafer with a concave-convex pattern on its surface, it is impossible to accurately evaluate the contact angle of the
水滴之接觸角之評價係如JIS R 3257「基板玻璃表面之潤濕性試驗方法」所記載那樣，藉由於樣品(基材)表面滴加數μl水滴，測定水滴與基材表面所成之角度而進行。但是，於具有圖案之晶圓之情形時，接觸角變得非常大。其原因在於：產生Wenzel效應或Cassie效應，接觸角受到基材之表面形狀(粗糙度)之影響，使得表觀上之水滴之接觸角增大。The evaluation of the contact angle of water droplets is as described in JIS R 3257 "Test method for wettability of substrate glass surface". The angle between the water droplet and the surface of the substrate is measured by adding a few μl of water droplets to the surface of the sample (substrate). And proceed. However, in the case of patterned wafers, the contact angle becomes very large. The reason is that the Wenzel effect or the Cassie effect is generated, and the contact angle is affected by the surface shape (roughness) of the substrate, which increases the apparent contact angle of the water droplets.
因此，於本實施例中，將上述組合物之蒸氣供給至表面平滑之晶圓，於晶圓表面形成保護膜，將該保護膜視為於表面形成有凹凸圖案之晶圓的表面所形成之保護膜，進行各種評價。再者，於本實施例中，使用於表面平滑之矽晶圓上具有SiO2 層之「附有SiO2 膜之晶圓」作為表面平滑之晶圓。Therefore, in this embodiment, the vapor of the above composition is supplied to a wafer with a smooth surface, a protective film is formed on the surface of the wafer, and the protective film is regarded as being formed on the surface of the wafer with the uneven pattern formed on the surface The protective film is subjected to various evaluations. Furthermore, in this embodiment, a "wafer with SiO 2 film" having an SiO 2 layer on a silicon wafer with a smooth surface is used as a wafer with a smooth surface.
詳細情況如下所述。以下記載評價方法、組合物之製備、使用組合物之蒸氣的晶圓之表面處理方法、評價結果。The details are as follows. The following describes the evaluation method, the preparation of the composition, the surface treatment method of the wafer using the vapor of the composition, and the evaluation result.
[評價方法] (A)組合物之化學穩定性評價 將組合物之原料加以混合後，目視觀察於45℃下靜置後之組合物之外觀，將於1週後並不析出不溶物或生成沈澱者記為『◎』，將雖然於1日之靜置後並不析出不溶物或生成沈澱但於1週後析出不溶物或生成沈澱者記為『○』，將雖然於4小時之靜置後並不析出不溶物或生成沈澱但於1日之靜置後析出不溶物或者生成沈澱者記為『△』。又，將組合物之原料加以混合後，於45℃下進行靜置，將於4小時以內析出不溶物或者生成沈澱者記為『×』(不合格)。[Evaluation method] (A) Evaluation of the chemical stability of the composition After mixing the raw materials of the composition, visually observe the appearance of the composition after standing at 45°C. If no insoluble matter or precipitate is formed after 1 week, it will be marked as "◎". No insoluble matter or precipitate formed after standing, but insoluble matter or precipitate formed after 1 week was recorded as "○". Although no insoluble matter or precipitate formed after standing for 4 hours, it was on 1st day. After standing still, insoluble matter or precipitation is recorded as "△". In addition, after mixing the raw materials of the composition, it was allowed to stand still at 45°C, and those that precipitated insoluble matter or formed precipitates within 4 hours were recorded as "×" (unacceptable).
(B)形成於晶圓表面之保護膜之接觸角評價(撥水性賦予效果之評價) 於形成有保護膜之晶圓表面上放置純水約2 μl，藉由接觸角計(協和界面科學製造：CA-X型)測定水滴與晶圓表面所成之角(接觸角)，將70°以上作為合格。(B) Evaluation of the contact angle of the protective film formed on the surface of the wafer (evaluation of the effect of imparting water repellency) Place about 2 μl of pure water on the surface of the wafer with the protective film, and measure the angle (contact angle) between the water droplet and the wafer surface with a contact angle meter (manufactured by Kyowa Interface Science: CA-X). °Above is regarded as qualified.
[實施例1] (1)組合物之製備 將作為矽烷化劑之三甲基矽烷基二甲基胺[(CH3 )3 Si-N(CH3 )2 ](沸點約86℃，以後有時記載為「TMSDMA」)5 g、與作為溶劑之非環狀碳酸酯中之碳酸二甲酯[CH3 -O-CO-O-CH3 ](沸點約90℃)95 g加以混合而獲得組合物。將該組合物加以混合後根據上述(A)所記載之要點進行化學穩定性之評價，結果如表1所示那樣為◎。[Example 1] (1) Preparation of the composition Trimethylsilyldimethylamine [(CH 3 ) 3 Si-N(CH 3 ) 2 ] (boiling point of about 86°C, later When it is described as "TMSDMA") 5 g, mixed with 95 g of dimethyl carbonate [CH 3 -O-CO-O-CH 3 ] (boiling point about 90°C) in acyclic carbonate as a solvent to obtain combination. After mixing this composition, the chemical stability was evaluated based on the points described in (A) above. The result was as shown in Table 1 as ⓞ.
(2)矽晶圓之洗淨 將附有平滑之熱氧化膜之矽晶圓(表面具有厚度為1 μm之熱氧化膜層之Si晶圓)於1質量%之氫氟酸水溶液中以25℃浸漬10分鐘，於純水中以25℃浸漬1分鐘，於2-丙醇(iPA)中以25℃浸漬1分鐘。(2) Cleaning of silicon wafer A silicon wafer with a smooth thermal oxide film (Si wafer with a thermal oxide film layer with a thickness of 1 μm on the surface) is immersed in a 1% by mass hydrofluoric acid aqueous solution at 25°C for 10 minutes, and then in pure water It was immersed at 25°C for 1 minute, and immersed in 2-propanol (iPA) at 25°C for 1 minute.
(3)藉由蒸氣對矽晶圓表面之表面處理 於上述洗淨後，將矽晶圓以使iPA溢液之狀態水平地配置於蒸氣處理室，藉由後述之方法使上述所製備之溶液狀態之組合物蒸氣化，將該蒸氣供給至蒸氣處理室。繼而，於50℃以下之晶圓表面使蒸氣狀態變為上述組合物之液體狀態，將原本保持於晶圓表面之iPA置換為該組合物之液體。其後，將矽晶圓自蒸氣處理室取出，於iPA中以25℃浸漬1分鐘。最後，將矽晶圓自iPA取出，對其吹送空氣，從而去除表面之iPA。(3) Surface treatment of silicon wafer surface by steam After the above-mentioned cleaning, the silicon wafer is placed horizontally in the steam treatment chamber in the state of iPA overflow, and the composition in the solution state prepared above is vaporized by the method described below, and the steam is supplied to the steam treatment room. Then, the vapor state of the wafer surface below 50°C is changed to the liquid state of the above composition, and the iPA originally held on the wafer surface is replaced with the liquid of the composition. After that, the silicon wafer was taken out of the vapor processing chamber and immersed in iPA at 25°C for 1 minute. Finally, the silicon wafer is taken out from the iPA, and air is blown to it to remove the iPA on the surface.
上述組合物之蒸氣之供給係以如下之方式進行。於加熱至145℃之蒸氣化室中，一面使氮氣以2 dm3 /分鐘之流量流動，一面以0.01 g/秒之滴加速度滴加上述所製備之溶液狀態之組合物，使滴加之組合物立即全部蒸氣化，藉由氮氣流動將該組合物蒸氣供給至蒸氣處理室。進行60秒之該處理。The steam supply of the above composition is carried out in the following manner. In a vaporization chamber heated to 145°C, while allowing nitrogen to flow at a flow rate of 2 dm 3 /min, while dropping the composition in the solution state prepared above at a dropping rate of 0.01 g/sec, the composition was added dropwise It was completely vaporized at once, and the composition vapor was supplied to the vapor treatment chamber by the flow of nitrogen. Perform this treatment for 60 seconds.
根據上述(B)所記載之要點實施接觸角評價，結果如表1所示，表面處理前之初始接觸角(即，於僅僅未進行上述之藉由蒸氣之表面處理，除此以外實施了相同之處理之情形時之接觸角)未達10°之，表面處理後之接觸角變為81°，顯示出撥水性賦予效果。The contact angle evaluation was performed according to the points described in (B) above. The results are shown in Table 1. The initial contact angle before the surface treatment (that is, the surface treatment by steam was not performed as described above, except that the same was performed). When the contact angle in the case of the treatment is less than 10°, the contact angle after surface treatment becomes 81°, showing the effect of imparting water repellency.
[表1]
[實施例2] 使用非環狀碳酸酯中之碳酸二乙酯[CH3 CH2 -O-CO-O-CH2 CH3 ](沸點約126℃)代替實施例1所使用之溶劑，除此以外與實施例1同樣地製備組合物，進行表面處理，並進行評價。將結果示於表1。[Example 2] Diethyl carbonate [CH 3 CH 2 -O-CO-O-CH 2 CH 3 ] (boiling point about 126°C) in acyclic carbonate was used instead of the solvent used in Example 1, except Otherwise, the composition was prepared in the same manner as in Example 1, and the surface treatment was performed and evaluated. The results are shown in Table 1.
[實施例3] 作為組合物之原料，使用作為矽烷化劑之TMSDMA 5 g、作為溶劑之非環狀碳酸酯中之碳酸二甲酯45 g與非環狀碳酸酯中之碳酸二乙酯50 g，除此以外與實施例1同樣地製備組合物，進行表面處理，並進行評價。將結果示於表1。[Example 3] As the raw material of the composition, 5 g of TMSDMA as a silylation agent, 45 g of dimethyl carbonate in acyclic carbonate as a solvent, and 50 g of diethyl carbonate in acyclic carbonate as a solvent are used. The composition was prepared in the same manner as in Example 1, and the surface treatment was performed and evaluated. The results are shown in Table 1.
[實施例4] 作為組合物之原料，使用作為矽烷化劑之TMSDMA 5 g、作為溶劑之環狀碳酸酯中之碳酸丙二酯(沸點約240℃)10 g、與非環狀碳酸酯中之碳酸二乙酯85 g，除此以外與實施例1同樣地製備組合物，進行表面處理，並進行評價。將結果示於表1。[Example 4] As the raw materials of the composition, 5 g of TMSDMA as a silylation agent, 10 g of propylene carbonate (boiling point about 240°C) in a cyclic carbonate as a solvent, and diethyl carbonate in a non-cyclic carbonate are used 85 g, except that the composition was prepared in the same manner as in Example 1, and the surface treatment was performed and evaluated. The results are shown in Table 1.
[實施例5] 作為組合物之原料，使用作為矽烷化劑之TMSDMA 5 g、作為溶劑之環狀碳酸酯中之碳酸丙二酯45 g、與非環狀碳酸酯中之碳酸二乙酯50 g，除此以外與實施例1同樣地製備組合物，進行表面處理，並進行評價。將結果示於表1。[Example 5] As the raw materials of the composition, 5 g of TMSDMA as a silylation agent, 45 g of propylene carbonate in a cyclic carbonate as a solvent, and 50 g of diethyl carbonate in a non-cyclic carbonate are used. The composition was prepared in the same manner as in Example 1, and the surface treatment was performed and evaluated. The results are shown in Table 1.
[實施例6] 作為組合物之原料，使用作為矽烷化劑之TMSDMA 2 g、與作為溶劑之碳酸二甲酯98 g，除此以外與實施例1同樣地製備組合物，進行表面處理，並進行評價。將結果示於表1。[Example 6] As the raw material of the composition, 2 g of TMSDMA as a silylation agent and 98 g of dimethyl carbonate as a solvent were used, except that the composition was prepared in the same manner as in Example 1, and subjected to surface treatment and evaluation. The results are shown in Table 1.
[實施例7] 作為組合物之原料，使用作為矽烷化劑之TMSDMA 8 g、與作為溶劑之碳酸二甲酯92 g，除此以外與實施例1同樣地製備組合物，進行表面處理，並進行評價。將結果示於表1。[Example 7] As the raw materials of the composition, 8 g of TMSDMA as a silylation agent and 92 g of dimethyl carbonate as a solvent were used, except that the composition was prepared in the same manner as in Example 1, and subjected to surface treatment and evaluation. The results are shown in Table 1.
[實施例8] 作為組合物之原料，使用作為矽烷化劑之TMSDMA 11 g、與作為溶劑之碳酸二甲酯88 g，除此以外與實施例1同樣地製備組合物，進行表面處理，並進行評價。將結果示於表1。[Example 8] As the raw material of the composition, 11 g of TMSDMA as a silylation agent and 88 g of dimethyl carbonate as a solvent were used, except that the composition was prepared in the same manner as in Example 1, and subjected to surface treatment and evaluation. The results are shown in Table 1.
[比較例1] 作為組合物之原料，使用作為並不相當於通式[1]之矽烷化劑(以後，有時記載為「其他矽烷化劑」)之1,1,1,2,2,2-六甲基二矽氮烷(沸點約125℃)(以後，有時記載為「HMDS」)1.5 g、作為觸媒之三氟乙酸三甲基矽烷酯(沸點約90℃)(以後，有時記載為「TMSTFA」)0.1 g、作為溶劑之3M Japan股份有限公司製造之氫氟醚(Novec(商標) HFE-7100)(沸點約61℃) 95.4 g與丙二醇單甲醚乙酸酯(沸點約146℃)(以後，有時記載為「PGMEA」)3 g，代替通式[1]所表示之化合物，除此以外與實施例1同樣地製備組合物，進行表面處理，並進行評價。將結果示於表1。[Comparative Example 1] As the raw material of the composition, 1,1,1,2,2,2-hexamethyl, which is not equivalent to the silylation agent of the general formula [1] (hereinafter, sometimes referred to as "other silylation agent") is used Disilazane (boiling point about 125°C) (hereafter, sometimes referred to as "HMDS") 1.5 g, trimethylsilyl trifluoroacetate (boiling point about 90°C) as a catalyst (hereafter, sometimes referred to as "TMSTFA") 0.1 g, as a solvent, 3M Japan Co., Ltd. manufactures hydrofluoroether (Novec (trademark) HFE-7100) (boiling point about 61°C) 95.4 g and propylene glycol monomethyl ether acetate (boiling point about 146°C) ) (Hereinafter, it may be described as "PGMEA") 3 g, except that instead of the compound represented by the general formula [1], a composition was prepared in the same manner as in Example 1, and subjected to surface treatment and evaluation. The results are shown in Table 1.
[比較例2] 作為組合物之原料，使用作為其他矽烷化劑之HMDS 1.5 g、作為觸媒之三氟乙酸(沸點約72℃)(以後，有時記載為「TFA」) 0.1 g、作為溶劑之Novec(商標)HFE-7100 95.4 g與PGMEA 3 g，代替通式[1]所表示之化合物，除此以外與實施例1同樣地製備組合物，進行表面處理，並進行評價。將結果示於表1。[Comparative Example 2] As the raw material of the composition, 1.5 g of HMDS as another silylation agent, trifluoroacetic acid (boiling point about 72°C) as a catalyst (hereinafter, sometimes referred to as "TFA") 0.1 g, and Novec (trademark) as a solvent ) 95.4 g of HFE-7100 and 3 g of PGMEA, except that the compound represented by the general formula [1] was replaced, a composition was prepared in the same manner as in Example 1, and the surface treatment was performed and evaluated. The results are shown in Table 1.
[比較例3] 作為組合物之原料，使用作為其他矽烷化劑之HMDS 1.5 g、作為觸媒之三氟乙酸酐(沸點約40℃)(以後，有時記載為「TFAA」) 0.1 g、作為溶劑之Novec(商標)HFE-7100 95.4 g與PGMEA 3 g，代替通式[1]所表示之化合物，除此以外與實施例1同樣地製備組合物，進行表面處理，並進行評價。將結果示於表1。[Comparative Example 3] As the raw materials of the composition, 1.5 g of HMDS as another silylation agent, trifluoroacetic anhydride (boiling point about 40°C) as a catalyst (hereinafter, sometimes referred to as "TFAA") 0.1 g, as a solvent Novec ( Trademark) 95.4 g of HFE-7100 and 3 g of PGMEA, except that the compound represented by the general formula [1] was replaced, a composition was prepared in the same manner as in Example 1, and the surface treatment was performed and evaluated. The results are shown in Table 1.
[比較例4] 作為組合物之原料，使用作為其他矽烷化劑之HMDS 1.5 g、作為觸媒之TMSTFA 0.1 g、作為溶劑之1,2-二氯-3,3,3-三氟-1-丙烯(沸點約54℃)(以後，有時記載為「DCTFP」) 95.4 g與PGMEA 3 g，代替通式[1]所表示之化合物，除此以外與實施例1同樣地製備組合物，進行表面處理，並進行評價。將結果示於表1。[Comparative Example 4] As the raw material of the composition, 1.5 g of HMDS as other silylation agent, 0.1 g of TMSTFA as catalyst, and 1,2-dichloro-3,3,3-trifluoro-1-propene as solvent (boiling point approximately 54°C) (hereinafter, sometimes referred to as "DCTFP") 95.4 g and PGMEA 3 g, instead of the compound represented by the general formula [1], except that the composition was prepared in the same manner as in Example 1, and the surface treatment was performed. Make an evaluation. The results are shown in Table 1.
[比較例5] 作為組合物之原料，使用作為其他矽烷化劑之1,1,2,2-四甲基二矽氮烷(沸點約100℃)(以後，有時記載為「TMDS」) 1.5 g、作為觸媒之TMSTFA 0.1 g、作為溶劑之Novec(商標)HFE-7100 95.4 g與PGMEA 3 g，代替通式[1]所表示之化合物，除此以外與實施例1同樣地製備組合物，進行表面處理，並進行評價。將結果示於表1。[Comparative Example 5] As the raw material of the composition, 1,1,2,2-tetramethyldisilazane (boiling point about 100°C) (hereinafter, sometimes referred to as "TMDS") 1.5 g, which is another silylation agent, is used, as 0.1 g of TMSTFA as a medium, 95.4 g of Novec (trademark) HFE-7100 as a solvent, and 3 g of PGMEA, instead of the compound represented by the general formula [1], a composition was prepared in the same manner as in Example 1, and the surface treatment was performed. , And evaluate it. The results are shown in Table 1.
[比較例6] 作為組合物之原料，使用作為其他矽烷化劑之TMDS 1.5 g、作為觸媒之TFA 0.1 g、作為溶劑之Novec(商標)HFE-7100 95.4 g與PGMEA 3 g，代替通式[1]所表示之化合物，除此以外與實施例1同樣地製備組合物，進行表面處理，並進行評價。將結果示於表1。[Comparative Example 6] As the raw materials of the composition, use TMDS 1.5 g as other silylation agent, TFA 0.1 g as catalyst, Novec (trademark) HFE-7100 95.4 g and PGMEA 3 g as solvent, instead of the general formula [1]. Except for the compound, a composition was prepared in the same manner as in Example 1, and the surface treatment was performed and evaluated. The results are shown in Table 1.
[比較例7] 作為組合物之原料，使用作為矽烷化劑之TMSDMA 5 g、作為溶劑之環狀碳酸酯中之碳酸丙二酯60 g與非環狀碳酸酯中之碳酸二乙酯35 g，以此除此以外與實施例1同樣地製備組合物，進行表面處理，並進行評價。將結果示於表1。[Comparative Example 7] As the raw materials of the composition, 5 g of TMSDMA as a silylation agent, 60 g of propylene carbonate in cyclic carbonate as a solvent, and 35 g of diethyl carbonate in acyclic carbonate as the solvent are used, and so on. Except that, the composition was prepared in the same manner as in Example 1, and the surface treatment was performed and evaluated. The results are shown in Table 1.
對於實施例1～8及比較例1～7之組合物，根據上述(B)中記載之要點進行評價之撥水性賦予效果於所有組合物中同等，以接觸角計而言均為約80°。 又，關於各組合物，若對撥水性保護膜形成成分數進行比較，則如表1所示那樣，實施例1～8之組合物為1，另一方面，比較例1～6之組合物為2。 又，於組合物之溶劑總量中之非環狀碳酸酯之量為50～100質量%之範圍內的實施例1～8中，將組合物之原料加以混合後，於45℃下進行靜置，於4小時以內並不析出溶物或生成沈澱，顯示出化學穩定性，相對於此，於組合物之溶劑總量中之非環狀碳酸酯之量未達50質量%(37質量%)的比較例7中，將組合物之原料加以混合後，於45℃下進行靜置，確認於4小時以內析出不溶物，確認化學穩定性並不充分。For the compositions of Examples 1 to 8 and Comparative Examples 1 to 7, the water repellency imparting effect evaluated based on the points described in (B) above is equivalent to all compositions, and the contact angle is about 80°. . In addition, for each composition, when the number of components forming the water-repellent protective film is compared, as shown in Table 1, the composition of Examples 1 to 8 is 1. On the other hand, the composition of Comparative Examples 1 to 6 Is 2. In addition, in Examples 1-8 in which the amount of acyclic carbonate in the total solvent of the composition was in the range of 50-100% by mass, the raw materials of the composition were mixed and then statically performed at 45°C. It does not precipitate or form precipitates within 4 hours, showing chemical stability. In contrast, the amount of acyclic carbonate in the total solvent of the composition is less than 50% by mass (37% by mass). In Comparative Example 7 of ), after mixing the raw materials of the composition, it was allowed to stand still at 45°C, and it was confirmed that insoluble matter precipitated within 4 hours, and it was confirmed that the chemical stability was insufficient.
根據以上可知：根據本發明可提供撥水性保護膜形成成分之種類更少的蒸氣處理用之新穎組合物，其化學穩定性優異，且可發揮出與利用先前之(撥水性保護膜形成成分之種類較多之)組合物之蒸氣進行具有Si元素之晶圓表面之處理之情形同等的撥水性賦予效果；且可提供將上述新穎組合物之蒸氣用於撥水性保護膜之形成的具有Si元素之晶圓之表面處理方法。From the above, it can be seen that according to the present invention, a novel composition for steam treatment with fewer types of water-repellent protective film forming components can be provided, which has excellent chemical stability, and can perform and utilize the previous (one of the water-repellent protective film forming components). A wide variety of) The vapor of the composition is treated with the Si element on the surface of the wafer. The effect is equivalent to the water repellency imparting effect; and the vapor of the above novel composition is used for the formation of the water repellent protective film with Si element The surface treatment method of the wafer.
1‧‧‧晶圓
2‧‧‧晶圓表面之微細之凹凸圖案
3‧‧‧圖案之凸部
4‧‧‧圖案之凹部
5‧‧‧凹部之寬度
6‧‧‧凸部之高度
7‧‧‧凸部之寬度
8‧‧‧保持於凹部4之液體
9‧‧‧組合物之蒸氣
10‧‧‧保持於凹部4之液體
11‧‧‧保護膜1‧‧‧
圖1係表面為具有微細之凹凸圖案2之面的晶圓1之立體模式圖。
圖2係表示圖1中之a-a'剖面之一部分者。
圖3係向保持有液體之凹部供給組合物之蒸氣之狀態之模式圖。
圖4係於形成有保護膜之凹部4保持有液體之狀態之模式圖。FIG. 1 is a three-dimensional schematic diagram of a
1‧‧‧晶圓 1‧‧‧Wafer
3‧‧‧圖案之凸部 3‧‧‧The convex part of the pattern
4‧‧‧圖案之凹部 4. The concave part of the pattern
10‧‧‧保持於凹部4之液體
10‧‧‧Liquid held in
11‧‧‧保護膜 11‧‧‧Protective film
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| JP2018072809 | 2018-04-05 |
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| TW108111659A TWI740122B (en) | 2018-04-05 | 2019-04-02 | Surface treatment method of wafer and composition used in the method |
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| US (1) | US11603485B2 (en) |
| JP (1) | JP7252478B2 (en) |
| KR (1) | KR102391370B1 (en) |
| CN (1) | CN111886676A (en) |
| SG (1) | SG11202009171XA (en) |
| TW (1) | TWI740122B (en) |
| WO (1) | WO2019193967A1 (en) |
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| KR20210092297A (en) * | 2018-11-22 | 2021-07-23 | 샌트랄 글래스 컴퍼니 리미티드 | Bevel treatment agent composition and manufacturing method of wafer |
| KR20220106131A (en) * | 2019-11-29 | 2022-07-28 | 샌트랄 글래스 컴퍼니 리미티드 | Chemical solution for forming a protective film and cleaning method for wafers |
| JP7446097B2 (en) * | 2019-12-06 | 2024-03-08 | 東京応化工業株式会社 | Surface treatment agent and surface treatment method |
| WO2022181530A1 (en) | 2021-02-26 | 2022-09-01 | セントラル硝子株式会社 | Surface treatment composition and method for producing wafer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201232196A (en) * | 2010-12-28 | 2012-08-01 | Central Glass Co Ltd | Wafer washing method |
| TW201842148A (en) * | 2017-03-24 | 2018-12-01 | 美商富士軟片電子材料美國股份有限公司 | Surface treatment methods and compositions therefor |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53106077A (en) | 1977-02-28 | 1978-09-14 | Nippon Steel Corp | Temperature measuring method of drawing materials in drawing line |
| JPH0742255B2 (en) | 1986-11-25 | 1995-05-10 | 三菱瓦斯化学株式会社 | Method for producing quaternary ammonium bicarbonate |
| KR20170092714A (en) | 2008-10-21 | 2017-08-11 | 도오꾜오까고오교 가부시끼가이샤 | Surface treatment liquid, surface treatment method, hydrophobilization method, and hydrophobilized substrate |
| JP5483858B2 (en) | 2008-10-21 | 2014-05-07 | 東京応化工業株式会社 | Surface treatment liquid, hydrophobization method, and hydrophobized substrate |
| JP5648053B2 (en) | 2010-06-30 | 2015-01-07 | セントラル硝子株式会社 | Chemical solution for forming wafer pattern protective film, method for preparing chemical solution, and wafer processing method |
| US8828144B2 (en) | 2010-12-28 | 2014-09-09 | Central Grass Company, Limited | Process for cleaning wafers |
| JP2013102109A (en) * | 2011-01-12 | 2013-05-23 | Central Glass Co Ltd | Liquid chemical for forming protecting film |
| JP5941623B2 (en) * | 2011-03-25 | 2016-06-29 | 東京エレクトロン株式会社 | Processing method and storage medium |
| WO2013069499A1 (en) * | 2011-11-11 | 2013-05-16 | セントラル硝子株式会社 | Wafer surface-treatment method and surface-treatment liquid, and surface-treatment agent, surface-treatment liquid, and surface-treatment method for silicon-nitride-containing wafers |
| JP2013168583A (en) | 2012-02-16 | 2013-08-29 | Toagosei Co Ltd | Surface treatment agent and surface treatment method |
| JP6462462B2 (en) * | 2015-04-01 | 2019-01-30 | 東芝メモリ株式会社 | Substrate processing apparatus and substrate processing method |
| JP6592303B2 (en) | 2015-08-14 | 2019-10-16 | 株式会社Ｓｃｒｅｅｎホールディングス | Substrate cleaning method and substrate cleaning apparatus |
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2019
- 2019-03-19 KR KR1020207031373A patent/KR102391370B1/en active IP Right Grant
- 2019-03-19 SG SG11202009171XA patent/SG11202009171XA/en unknown
- 2019-03-19 US US17/040,902 patent/US11603485B2/en active Active
- 2019-03-19 WO PCT/JP2019/011387 patent/WO2019193967A1/en active Application Filing
- 2019-03-19 CN CN201980020638.2A patent/CN111886676A/en active Pending
- 2019-03-19 JP JP2020511687A patent/JP7252478B2/en active Active
- 2019-04-02 TW TW108111659A patent/TWI740122B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201232196A (en) * | 2010-12-28 | 2012-08-01 | Central Glass Co Ltd | Wafer washing method |
| TW201842148A (en) * | 2017-03-24 | 2018-12-01 | 美商富士軟片電子材料美國股份有限公司 | Surface treatment methods and compositions therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| SG11202009171XA (en) | 2020-10-29 |
| CN111886676A (en) | 2020-11-03 |
| US20210009882A1 (en) | 2021-01-14 |
| JPWO2019193967A1 (en) | 2021-06-24 |
| KR102391370B1 (en) | 2022-04-27 |
| US11603485B2 (en) | 2023-03-14 |
| WO2019193967A1 (en) | 2019-10-10 |
| JP7252478B2 (en) | 2023-04-05 |
| KR20200136999A (en) | 2020-12-08 |
| TW201943833A (en) | 2019-11-16 |
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